Design of an industrial process for the production of aniline by direct amination R.T. Driessen, P. Kamphuis, L. Mathijssen, R. Zhang, A.G.J.

Transcription

1 Design of an industrial process for the production of aniline by direct amination R.T. Driessen, P. Kamphuis, L. Mathijssen, R. Zhang, A.G.J. van der Ham, H. van den Berg, A.J. Zeeuw University of Twente, Faculty of Science and Technology, Enschede, The Netherlands, Huntsman Belgium BVBA, Everberg, Belgium 1

2 Aniline is a frequently used bulk chemical Precursor for MDA production MDA is used for MDI production 4,4-methylenedianiline (MDA) Aniline methylene diphenyl di-isocyanate (MDI) 2

3 The current aniline production needs to be improved, due to major drawbacks Conventional chemistry: Drawbacks: Low atomic efficiency Formation of acids Expensive raw materials T. Kahl et al., Ullmann s Encycl. Ind. Chem., (2000) B. Saha et al., Rev. Environ. Sci. Technol., 43, (2011) 3

4 The aim of the project is to design a process of direct amination of benzene to aniline benzene N-compound Aniline production by direct amination Protonated aniline (75 wt%) 250 kton/year MDI production MDI Project boundary Requirements: Location: Rotterdam Direct amination of benzene 250 kt/year 75 wt% protonated aniline 4

5 All design alternatives are kept, until sufficient basis for rejection Douglas method: Functions unit operations Development of alternatives J. M. Douglas, Conceptual design of chemical processes. McGraw-Hill (1988) Van den Berg et al., Direct amination of benzene for aniline production, CHISA

6 All design alternatives are kept, until sufficient basis for rejection Start Douglas method: Functions unit operations Background information Development of alternatives Feasible? No Alternative designs Yes Blackbox Feasible? No Data complete? No Detailed design Yes Yes Preliminary economic analysis Economics No Feasible? Feasible? No J. M. Douglas, Conceptual design of chemical processes. McGraw-Hill (1988) Van den Berg et al., Direct amination of benzene for aniline production, CHISA 2014 Yes Conceptual Design Yes Finalization 5

7 All design alternatives are kept, until sufficient basis for rejection Start Douglas method: Functions unit operations Background information Development of alternatives Feasible? No Alternative designs Yes Main choice Direct amination with 1. Hydroxylamine (NH 2 OH) Blackbox Data complete? Yes No Feasible? Detailed design Yes No 2. Ammonia (NH 3 ) Adverse equilibrium Preliminary economic analysis Feasible? No Economics Feasible? No J. M. Douglas, Conceptual design of chemical processes. McGraw-Hill (1988) Van den Berg et al., Direct amination of benzene for aniline production, CHISA 2014 Yes Conceptual Design Yes Finalization 5

8 The focus of this project is on hydroxylamine Reaction conditions: T = 70 C, P = 1 bar good conversion (68.5%), high selectivity (>99.9%) Mn-MCM-41 catalyst K.M. Parida et al., Appl. Catal., A., 351, (2008) 6

9 The focus of this project is on hydroxylamine Reaction conditions: T = 70 C, P = 1 bar good conversion (68.5%), high selectivity (>99.9%) Mn-MCM-41 catalyst Hydroxylamine is however expensive Hydroxylamine production included in scope N-compound Hydroxylamine production NH 2 OH Aniline production by direct amination Protonated aniline (75 wt%) 250 kton/year Project boundary Benzene K.M. Parida et al., Appl. Catal., A., 351, (2008) 6

10 Chemical reduction of nitric oxide is the most promising route to produce hydroxylamine N-compound Hydroxylamine production NH 2 OH Aniline production by direct amination Protonated aniline (75 wt%) 250 kton/year Project boundary Benzene Electrochemical reduction: T = 27 C, P = 1 bar, ζ = 17.6%, σ = 93% Chemical reduction: T = 25 C, P = 1 bar, ζ = 77%, σ > 85% Proven technology Platinum catalyst K. Otsuka et al., J. Electrochem. Soc., 143, 3491, (1996) R.E. Benson, et al. J. Am. Chem. Soc., 78, , (1956) T. Hara et al., Appl. Catal. A Gen., 320, (2007) 7

11 Due to low availability of nitric oxide, the production of nitric oxide is incorporated in the project boundary N-compound Nitric oxide production NO Hydroxylamine production NH 2 OH Aniline production by direct amination Protonated aniline (75 wt%) 250 kton/year Project boundary Benzene NO: Greenhouse gas Only low quantities commercially available Reaction conditions: T = 70 C, P = 1 bar η = 99% Proven technology in nitric acid production 5%-Rh-Pt catalyst M. Thiemann et al., Ullmann s Encycl. Ind. Chem., 24, (2012) 8

12 Proposed process 9

13 Proposed flowsheet Hydroxylamine production 20 C, 11.6 bar 35 C, 10.1 bar NH3, NO, N2, N2O 33 C, 1.5 bar S3 (pressure swing adsorption) Nitric oxide production NH3, NO, N2, N2O, Air 20 C, 1 bar Air 407 C, 12 bar NH3 R1, NH3 850 C, 11.8 bar, NH3 35 C, 11.6 bar S1 N2O, NO, N2, NH3 28 C, 11.6 bar R2, NH3, H +, Cl -,, NH3OH C, 10.5 bar, NH3, H +, Cl -,, NH3OH + S2, H +, Cl -, NH3OH C, 10.3 bar 20 C, 12 bar 188 C, 12 bar 35 C, 12 bar 35 C, 11.6 bar H +, Cl -,, 20 C, 11.6 bar, H +, Cl -, NH3OH + 70 C, 10.3 bar Aniline production Purge R3 H +,, Cl -, C6H6, C6H5NH3 +, C12H10, 165 C, 10.1 bar H +,, Cl -, C6H6, C6H5NH3 +, C12H10, S4, Cl -, H +, C6H5NH3 + Modeled with UniSim R410 (NRTL-PR) 70 C, 10.3 bar Purge C6H6 20 C, 10.3 bar 10

14 Proposed flowsheet Hydroxylamine production 20 C, 11.6 bar 35 C, 10.1 bar NH3, NO, N2, N2O 33 C, 1.5 bar S3 (pressure swing adsorption) Nitric oxide production NH3, NO, N2, N2O, Air 20 C, 1 bar Air 407 C, 12 bar NH3 R1, NH3 850 C, 11.8 bar, NH3 35 C, 11.6 bar S1 N2O, NO, N2, NH3 28 C, 11.6 bar R2, NH3, H +, Cl -,, NH3OH C, 10.5 bar, NH3, H +, Cl -,, NH3OH + S2, H +, Cl -, NH3OH C, 10.3 bar 20 C, 12 bar 188 C, 12 bar 35 C, 12 bar 35 C, 11.6 bar H +, Cl -,, 20 C, 11.6 bar, H +, Cl -, NH3OH + 70 C, 10.3 bar Aniline production Purge R3 H +,, Cl -, C6H6, C6H5NH3 +, C12H10, 165 C, 10.1 bar H +,, Cl -, C6H6, C6H5NH3 +, C12H10, S4, Cl -, H +, C6H5NH3 + Modeled with UniSim R410 (NRTL-PR) 70 C, 10.3 bar Purge C6H6 20 C, 10.3 bar 10

15 Proposed flowsheet Hydroxylamine production 20 C, 11.6 bar 35 C, 10.1 bar NH3, NO, N2, N2O 33 C, 1.5 bar S3 (pressure swing adsorption) Nitric oxide production NH3, NO, N2, N2O, Air 20 C, 1 bar Air 407 C, 12 bar NH3 R1, NH3 850 C, 11.8 bar, NH3 35 C, 11.6 bar S1 N2O, NO, N2, NH3 28 C, 11.6 bar R2, NH3, H +, Cl -,, NH3OH C, 10.5 bar, NH3, H +, Cl -,, NH3OH + S2, H +, Cl -, NH3OH C, 10.3 bar 20 C, 12 bar 188 C, 12 bar 35 C, 12 bar 35 C, 11.6 bar H +, Cl -,, 20 C, 11.6 bar, H +, Cl -, NH3OH + 70 C, 10.3 bar Aniline production Purge R3 H +,, Cl -, C6H6, C6H5NH3 +, C12H10, 165 C, 10.1 bar H +,, Cl -, C6H6, C6H5NH3 +, C12H10, S4, Cl -, H +, C6H5NH3 + Modeled with UniSim R410 (NRTL-PR) 70 C, 10.3 bar Purge C6H6 20 C, 10.3 bar 10

16 Proposed flowsheet Hydroxylamine production 20 C, 11.6 bar 35 C, 10.1 bar NH3, NO, N2, N2O 33 C, 1.5 bar S3 (pressure swing adsorption) Nitric oxide production NH3, NO, N2, N2O, Air 20 C, 1 bar Air 407 C, 12 bar NH3 R1, NH3 850 C, 11.8 bar, NH3 35 C, 11.6 bar S1 N2O, NO, N2, NH3 28 C, 11.6 bar R2, NH3, H +, Cl -,, NH3OH C, 10.5 bar, NH3, H +, Cl -,, NH3OH + S2, H +, Cl -, NH3OH C, 10.3 bar 20 C, 12 bar 188 C, 12 bar 35 C, 12 bar 35 C, 11.6 bar H +, Cl -,, 20 C, 11.6 bar, H +, Cl -, NH3OH + 70 C, 10.3 bar Aniline production Purge R3 H +,, Cl -, C6H6, C6H5NH3 +, C12H10, 165 C, 10.1 bar H +,, Cl -, C6H6, C6H5NH3 +, C12H10, S4, Cl -, H +, C6H5NH3 + Modeled with UniSim R410 (NRTL-PR) 70 C, 10.3 bar Purge C6H6 20 C, 10.3 bar 10

17 Proposed flowsheet Hydroxylamine production 20 C, 11.6 bar 35 C, 10.1 bar NH3, NO, N2, N2O 33 C, 1.5 bar S3 (pressure swing adsorption) Nitric oxide production NH3, NO, N2, N2O, Air 20 C, 1 bar Air 407 C, 12 bar NH3 R1, NH3 850 C, 11.8 bar, NH3 35 C, 11.6 bar S1 N2O, NO, N2, NH3 28 C, 11.6 bar R2, NH3, H +, Cl -,, NH3OH C, 10.5 bar, NH3, H +, Cl -,, NH3OH + S2, H +, Cl -, NH3OH C, 10.3 bar 20 C, 12 bar 188 C, 12 bar 35 C, 12 bar 35 C, 11.6 bar H +, Cl -,, 20 C, 11.6 bar, H +, Cl -, NH3OH + 70 C, 10.3 bar Aniline production Purge R3 H +,, Cl -, C6H6, C6H5NH3 +, C12H10, 165 C, 10.1 bar H +,, Cl -, C6H6, C6H5NH3 +, C12H10, S4, Cl -, H +, C6H5NH3 + Modeled with UniSim R410 (NRTL-PR) 70 C, 10.3 bar Purge C6H6 20 C, 10.3 bar 10

18 Due to the PSA purge 27% of the atomic nitrogen is lost 11

19 No atomic carbon is lost in the process 12

20 Due to the water purge, 14.1% of atomic hydrogen is lost 13

21 Due to an excess of energy it is possible to produce a considerable amount of steam Reactor ΔT ad ( C) R1 749 R2 505 R3 84 Steam Q (MW) F (ton/h) High pressure (40 bar) Medium pressure (10 bar) 22.5 Low pressure (3.5 bar)

22 An overview of the costs and revenues shows that the process is profitable Total revenue = 418 M$/year 11% 4% 5% 6% 2% Based on: Material cost factor Hand factor, e.g. piping Location 72% Variable Production Cost Fixed Production Cost General Expenses Depreciation Profit Profit taxes CAPEX (M$) 460 Return on investment (ROI) (%) 5.5 Payback period (PBP) (years) 8 Profit (M$/year) 26 Profit margin (%) 6 15

23 Improving the separation efficiency or conversion in hydroxylamine reactor can reduce the nitric oxide loss Selectively separate hydrogen and nitric oxide from separator (S2) outlet Selectively separate nitric oxide from the purge Choose a different catalyst Increase conversion H 2 H 2 NH 3, NO, N 2, N 2 O 20 C, 11.6 bar 35 C, 10.1 bar 33 C, 1.5 bar S3 (pressure swing adsorption) NH 3, NO, N 2, N 2 O, H 2 from nitric oxide production N 2 O, NO, N 2, NH 3 28 C, 11.6 bar R2 N 2 O, NO, N 2, H 2 O, NH 3, H +, Cl -, H 2, NH 3 OH C, 10.5 bar N 2 O, NO, N 2, H 2 O, NH 3, H +, Cl -, H 2, NH 3 OH + S2 H 2 O, H +, Cl -, NH 3 OH C, 10.3 bar to aniline production 16

24 Burning ammonia to obtain nitric oxide is not energetically efficient, instead an alternative production route should be investigated Energetically not favorable o >28 GJ per tonne NH 3 (via Haber-Bosch) T = C, P = bars η = 1.5% N. Cherkasov et al. Chem. Eng. Process, 90, (2015) M. Appl, Ullmann s Encycl. Ind. Chem., (2011) 17

25 The process design still has an information gap Investigate kinetics for reactors for sound reactor design Detailed engineering of separation steps More effort on process modelling (e.g. electrolytic thermodynamic model) 18

26 Conclusion The designed process is technologically feasible, but economically it does not meet industry guidelines. Economically: ROI<20% Capex: 460 M$ Revenue: 420 M$/year Technically: Atomic efficiency (C=100%, N = 72%, H = 86%) Formation of high quality steam Proven technologies Integration with MDI production Raw materials remain expensive 19

27 Conclusion The designed process is technologically feasible, but economically it does not meet industry guidelines. Economically: ROI<20% Capex: 460 M$ Revenue: 420 M$/year Technically: Atomic efficiency (C=100%, N = 72%, H = 86%) Formation of high quality steam Proven technologies Integration with MDI production Raw materials remain expensive 19

28 Conclusion The designed process is technologically feasible, but economically it does not meet industry guidelines. Economically: ROI<20% Capex: 460 M$ Revenue: 420 M$/year Technically: Atomic efficiency (C=100%, N = 72%, H = 86%) Formation of high quality steam Proven technologies Integration with MDI production Raw materials remain expensive 19

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